Oxyranyle-triazoline thiones and their use as microbicides

ABSTRACT

Novel oxiranyl-triazolinethiones of the formula  
                 
 
     in which R 1 , R 2  and R 3  are each as defined in the description, a process for preparing the novel substances and their use as microbicides in crop protection and in the protection of materials.

The present invention relates to novel oxiranyl-triazolinetlhiones, to a process for their preparation and to their uses as microbicides.

[0001] It is already known that numerous azclylmethyl-oxirane derivatives have fungicidal properties (cf. EP-A 0 094 564, EP-A 0 196 038 and WO-A 96-38 440). Thus, for example, 3-(2-chloro-phenyl)-2-(4-fluoro-phenyl)-2-[(4,5-dihydro-5-thiono-1,2,4-triazol-1-yl)-methyl]-oxirane can be used for controlling fungi. The activity of this substance is good; however, it is sometimes unsatisfactory at low application rates.

[0002] This invention, accordingly, provides novel oxiranyl-triazolinethiones of the formula

[0003] in which R¹ requests alkyl having 1 to 4 carbons atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, optionally haolgen-subsituted cycloalkyl having 3 to 7 carbon atoms, naphthyl or phenyl which is optionally mono-to trisubstituted by identical or different substituents from the group consisting of halogen, nitro, phenyl, phenoxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon adoms, halogenoalky having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms and halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, R² represents phenyl which is optionally mono-to trisubstituted by identical or different substituents from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms and halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms and R³ represents alkoxyalkyl, isopropyl or n-dodecyl.

[0004] The substances according to the invention contain two asymmetrically substituted carbon atoms and can therefore be obtained in the form of diastereomers or enantionmiers. The present invention relates both to the individual isomers and to their mixtures.

[0005] Furthermore, it has been found that oxiranyl-triazolinethionics of the formula (1) or (1 a) are obtained when oxirane derivatives of the formula

[0006] in which R¹ and R² are each as defined above are reacted with isocyanates of the formula

R³-NCO  (III)

[0007] in which R³ is as defined above, if appropriate in the presence of a catalyst and if appropriate in the presence of a diluecnt.

[0008] Finally, it has been found that the novel oxiranyl-triazolinethiones of the formula (1) or (1 a) have very good microbicidal properties and can be use both in crop protection and in the protection of materials for controlling undesirable microorganisms.

[0009] Surprisingly, the oxiranyl-triazolinethiones of the fonnula (I) or (Ia) according to the invention have better inicrobicidal activity, in particular fungicidal activity, than the constitutionally most similar prior-art compounds of the same direction of action Thus, the substances according to the invention stirlpass 3-(2-chloro-plhenyl)-2-(4-fluoro-plhenyl)-2-[(4,5-dilydro-5-thiono-1,2,4-triazol-I -yl)-metlhyl]-oxirane with respect to the fungicidal properties.

[0010] The formula (I) or (la) provides a general definition of the oxiranlyl-triazolinetlhiones according to the invention. R¹ preferably represents methyl, ethyl, n-propyl, isopiropyl, n-buttyl, sec-butyl, iso-butyl, tert-butyl, fluoro-tert-butyl, difuoro-tert-butyl, cycloalkyl having 3 to 6 carbon atoms which is optionally mono-to tristubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine, preferably represents naphthyl or preferably represents phenyl which may be mono-to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, nitro, phenyl, phenoxy, methyl, ethyl, tert-butyl, metlhoxy, ethioxy, trifluoromethyl, trichloromethyl, difluoromethyl, dilluorochloromethyl, trifluoromethoxy, difluoromethoxy and tri fluoromethylthio, R² preferably represents phenyl which may be mono-to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, metlhyl, ethyl, isoprolpyl, tert-butyl, methioxy, ethoxy, trifluorometllyl, triclhloromethyl, difluorometlhyl, difluorochloromethyl, trifuorometlhoxy, difluoromethloxy and trifluorometlhylthio, and R³ preferably represents alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety and also preferably represents isopropyl or n-dodecyl.

[0011] Particular preference is given to oxiranyl-triazolinetthioncs of the formula (1) or (la) in which

[0012] R¹ represents phenlyl which may be mono-to trisuLtstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, nitro, phenyl, phenoxy, methiyl, ethyl, tert-butyl, mtchoxy, ethoxy, trifluoronietlyl, trichloroiiietliyl, (ifluoromiiethyl, di fluorochloromettiyl, trifluoromethoxy, difluoromethoxy and trifluoromethylthio, R² represents plicnyl which may be mono-to trisubstituted by identical or different subtstituenits from tlhc group consisting of fluorine, chlorine, bromine, methlyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl, difluorochloronmethyl, trifluoromethoxy, difluoromethloxy and trifluoromethylithio, and R³ represents alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety and also represents isopropyl or n-dodecyl.

[0013] The substituent definitions mentioned can be combined with one another at will. Moreover, individual definitions may not apply.

[0014] The oxirane derivatives required as starting materials for preparing the substances according to the invention can be present in the “thiono” form of the formula

[0015] or in the talitorneric “mercapto” form of the formula

[0016] It is therefore possible that the substances according to the invention can be derived both from the “thiono” form of the formula (II) and frorm the “mercapto” form of the formula (IIa). This means that the substances according to the invention are either present as substances of the formula

[0017] or of the formula

[0018] or as mixtures of the formulae (I) and (Ia).

[0019] Examples of substances according to the invention hvliiclh may be mentioned are the oxiranyl-triazoliiietliones listed in the table below. TABLE 1 (I)

or (Ia)

R¹ R² R³

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—C₂H₅

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—CH₃

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃ —O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—C—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

[0020] Using 3-(2-chloro-phenyl)-2-(4-fluoro-phenyl)-2-[(4,5-dihydro- 5-thiono-1 2,4-triazol-1-yl)-methyl]-oxirane as starting material and 3-ethoxy-propyl isocyanate as reaction component, the course of the process according to the invention can be illustrated by the scheme below.

[0021] The formula (II) or (IIa) provides a general definition of the oxirane derivatives required as starting materials for carrying out the process according to tile invention. In this formula, R¹ and R² preferably have those meanings which have already been mentioned in connection with the description of the substances of tile formnula (I) or (Ia) according to thle invention as being preferred for these radicals.

[0022] The oxiranie derivatives of thle formula (II) or (IIa) are already known (cf. WO-A 96-39 440).

[0023] The formula (III) provides a general definition of the isocyaniates required as reaction components for carrying out the process according to the inveIntion. In this fon-nula, R³ preferably has those meanings which have already been mentioned in connection with the description of thle substances of tile formula (I) according to the invention as being preferred for this radical.

[0024] The isocyaniates of the formula (III) are known or can be prepared by known methods.

[0025] Suitable catalysts for carrying out the process according to the invention are all reaction promoters which are customary for such reactions. Preference is given to using amines, such as triethylamine, pyridine, dimethylaminopyridine and diazabicyclo-undecene (DBU).

[0026] Suitable diluents for carrying out the process according to the invention are all inert organic solvents which are customary for such reactions. Preference is given to using aromatic hydrocarbons, such as toluene, xylene or decaline, also halogenated hydrocarbons, such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichlioroethane, moreover ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane or tetrahydrofuran, and furthermore nitriles, such as acetonitrile, propionitrile, n-or iso-butyronitrile.

[0027] When carrying out the process according to the invention, the reaction temperatures can be varied within a certain range. In general, the process is carried out at temperatures between −20° C. and +100° C., preferably between 0° C. and +80° C.

[0028] The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to carry out the process under elevated pressure or, if no highly volatile components are taking part in the reaction, also under reduced pressure.

[0029] When carrying out the process according to the invention, in general from I to 1.5 mol of isocyanate of the fomlula (III) and a small amount of catalyst are employed per mole of oxirane derivative of the formula (II) or (IIa). Work-up is carried out by customary methods. In general, the reaction mixture is concentrated under reduced pressure and the product that remains is freed from any impurities that may still be present by customary methods, for example by recrystallization or chromatography.

[0030] The compounds according to the invention have a potent microbicidal activity and can be employed for controlling undesirable microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.

[0031] Fungicides are employed in crop protection for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygoniycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

[0032] Bactericides are employed in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

[0033] Some pathogens causing fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation:

[0034]Xanthonionas species, such as, for example, Xanthomonas campestris pv. oryzae; Pseudomonas species, such as, for example, Pseudomonas syringae pv. lachrymans; Erwinia species, such as, for example, Erwinia amylovora; Pythium species, such as, for example, Pythium ultimum; Phytophtlhora species, such as, for example, Phytoplhthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis; Plasmopara species, such as, for example, Plasmopara viticola; Bremia species, such as, for example, Bremia lactucae, Peronoslpora species, such as, for example, Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, Erysiphe graminis; Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; Podosphaera species, such as, for example, Podosphaera leucotricha; Venturia species, such as, for example, Venturia inaequalis; Pyrenophora species, such as, for example, Pyrenophora tercs or P. graminea (conidia form: Drechslera, syn: Helminthosporium); Cochlioboltis species, such as, for example, Cochiliobolus sativus (conidia form: Drechslera, syn: Helminthosporium); Uromyces species, such as, for example, Uromyces appendiculatus; Puccinia species, such as, for example, Puccinia recondita; Sclerotinia species, such as, for example, Sclerotinia sclerotiorum Tilletia species, such as, for example, Tilletia caries; Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusarium culmorum; Botrytis species, such as, for example, Botrytis cinerea; Septoria species, such as, for example, Septoria nodorum; Leptosphiaeria species, such as, for example, Leptosphaeria nodorum; Cercospora species, such as, for example, Cercospora canescens; Alternaria species, such as, for example, Altemaria brassicae; and Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

[0035] The fact that the active compounds are well tolerated by plants at the concentrations required for controlling plant diseases permits the treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

[0036] The active compounds according to the invention can be employed in particular for controlling Pyticularia oryzae on rice and for controlling cereal diseases, such as Puccinia, Erysipie and Fusarium species. Moreover, the substances according to the invention can be used successfully against Venturia, Podosphaera and Sphaerotheca. They also have very good in-vitro action.

[0037] The active compounds according to the invention may also be employed to increase the yield of crops. Moreover, they have low toxicity and are well tolerated by plants.

[0038] In the protection of materials, the compounds according to the invention can be employed for protecting industrial materials against infection with, and destruction by, undesired microorganisms.

[0039] Industrial materials in the present context are understood as meaning non-living materials which have been prepared for use in industry. For example, industrial materials which are intended to be protected by active compounds according to the invention from microbial change or destruction can be adhesives, sizes, paper and board, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be infected with, or decomposed by, microorganisms. Parts of production plants, for example cooling-water circuits, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected. Industrial materials which may be mentioned within the scope of the present invention are preferably adhesives, sizes, paper and board, leather, wood, paints, cooling lubricants and heat-transfer liquids, particularly preferably wood.

[0040] Microorganisms capable of degrading or changing the industrial materials which may be mentioned are, for example, bacteria, fungi, yeasts, algae and slime organisms. The active compounds according to the invention preferably act against fungi, in particular moulds, wood-discolouring and wood-destroying fungi (Basidiomycetes), and against slime organisms and algae.

[0041] Microorganisms of the following genera may be mentioned as examples: Alternaria, such as Altemaria tentis, Aspergillus, such as Aslpergillus niger, Chaetomium, such as Chaetomium globosum, Coniophora, such as Coniophora puetania, Lentinus, such as Lentinus tigriitis, Pcenicilliutmi, such as Penicillium glaucum, Polyponis, such as Polyponis vcrsicolor, Aureobasidium, such as Aureobasidium pullulans, Sclerophoma, such as Sclerophoma pityophilIa, Trichoderma, such as Trichioderma viride, Eschierichia, such as Eschericihia coli, Pseudomonas, such as Pseudomonas aeruginosa, and Staphylococcus, such as Staphylococcus aureus.

[0042] Depending on their particular physical and/or chemical properties, the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and microencapsulations in polymeric substances and in coating compositions for seeds, and ULV cool and warm fogging formulations.

[0043] These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam fonners. If the extender used is water, it is also possible to use for example organic solvents as auxiliary solvents. The following are mainly suitable as liquid solvents: aromatics such as xylene, toluene or alkylnaptlilialenies, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as clilorobenizenies, cliloroethylenes or methylcne chloride, alipphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanlol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylfoniamide or dimethiyl sulphioxide, or else wvater. Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals such as kaolins, clays, talc, chalk, quartz, attalpulgite, monitirorillonite or cliatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates. Suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.

[0044] Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

[0045] It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phtlialocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

[0046] The formulations generally comprise between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

[0047] The active compounds according to the invention can be used as such or, in their formulations, also mixed with known fungicides, hactcricidcs, acaricides, nemiiaticides or insecticides in order thus, for example, to Widen the spectrum of action or to prevent development of resistance. In many cases, synergistic effects are achieved here, i.e. the activity of the mixture exceeds the activity of the individual components.

[0048] Examples of co-components in mixtures are the following compounds:

[0049] Fungicides: aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl, bialaphos, binapacryl, biplienyl, bitertanol, blasticidini-S, bromuconazole, bupirimate, buthiobate, calcium polysuiphide, capsimycin, captafol, captan, carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole, chlioroneb, chloropicrin, chlorotlalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram, debacarb, dichlioroplhen, diclobutrazole, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimelhonlorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon, edifenplios, epoxiconazole, etaconazole, etlhirimol, etridiazole, famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, fertiam, ferimzone, fluazinam, flumetover, fluoromide, fluquinconazole, flurprimidol, flusilazole, flisulfaiiiide, flutolaniil, flutriafol, folpet, fosetyl-aluminitim, fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr, fuircarbonil, furconazole, furconazole-cis, funnecyclox, guazatine, hexaciilorobeiizene, hexaconazole, hymexazole, imazalil, imibenconiazole, iminoctadine, iminoctadine albesilatc, iminoctadine triacetate, iodocarb, ipconazole, iprobcnfos (IBP), iprodione, irmamnycin, isoprothiolane, isovaledione, kasugamycini, kresoxim-inctliyl, copper preparations, suclh as: copper hydroxide, copper naphthenate, copper oxychlioricle, copper sulplhate, copper oxide, oxitie-copper and Bordeaux mixture, mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, mnethfuroxam, mctiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin, nickel dimetilyidithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfentlliin, paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine-sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinconazole, quintozene (PCNB), sulphur and sulphur preparations, tebuconazole, tecloftalain, tecnazene, tetcyclasis, tetraconazole, thiabendazole, thicyofen, thiifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricilamide, tricyclazole, tridemorph, triflumizole, triforine, triticotiazole, Linicoiiazole, validarnycin A, vinclozolin, viniconazole, zarilamide, zineb, zirain and also Dagger G, OK-8705, OK-8801, α-(1,1-dimethylethlyl)-β-(2-plienoxyethyl)- 1H-1,2,4-triazole-1-ethanol, α-(2,4-dichlorophenyl)-β-fluoro-b-propyl-1H-1,2,4-triazoIe-1 -etlianol, α-(2,4-dichlIoropihciiyl)-β-methoxy-a-methyl-H1,2,4-triazole-1-ethanol, α-(5-methyl-1,3-dioxan5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene-]-1H-1,2,4-triazole-1-ethanol, (5RS,6RS)-6-hydroxy-2,2,7,7-tetranietihyl-5-( 1H-1,2,4-triazol-1-yl)-3-octanone, (E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide, isopropyl {2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate, 1-(2,4-dichlorophenyl)-2-(1H,1,2,4-triazol-1-yl)-ethanone ◯-(phenylmenthyl) oxime, 1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione, 1-[(3,5-diclhlorophenyl)-3-(2-propenyl)-2,5-pyrrold(1incdione, 1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene, 1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole, 1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole, 1-[-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole, 1-methyl-5-nonyl-2-(phenlylmethyl)-3-pyrrolidinole, 2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide, 2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropaiiecarboxamide, 2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate, 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, 2,6-dicliloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide, 2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole, 2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole, 2-[[6-deoxy-4-◯-(4-◯-methyl-Γ-D-glycopyranosyl)-a-D-glucopyranosyl]-aminol]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile, 2-amninobutane, 2-bromo-2-(bromomethyl)-pentanedinitrile, 2-chltoro-N-(2,3-dihydro-1,1,3-trimethyl-III-inden-4-yl)-3-pyridinecarboxamide, 2-cloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide, 2-phenylphenol (OPP), 3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-III-pyrrole-2,5-dione, 3,5-dictiloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide, 3-(1,1 -dimethlypropyl-1-oxo-III-indene-2-carbonitrile, 3[2-(4-chlorophenyl)-5-ethoxy-3-isoxazoldinyl]-pyridine, 4-chloro-2-cyano-N,N-dimethyl-5-(4-methyphenyl)-1H-imidazole-1-sulphonamide, 4-methyl-tetrazolo[1 ,5-a]quinazolin-5(4H)-one, 8-(1,1 -dimenthylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine, 8-hydroxyquinoline sulphate, 9H-xanthlene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide, bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate, cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol, cis-4-[3 -[4-(1,1 -dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride, ethyl [(4-chlorophenyl)-azo]-cyanoacetate, potassium hydrogen carbonate, methanetetrathiol sodium salt, methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate, methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate, methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate, N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarbox am ide, N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide, N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyt)-acetamide, N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulplhonamide, N-(4-cycloliexylphenyl)-1,4,5,6-tetralhydro-2-pyrimidinamine, N-(4-hexylphenyl)- 1,4,5,6-tetrahydro-2-pyrimidiniamine, N-(5-chloro-2-methoxyplenyl) )-2 -methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide, N-(6-methoxy)-3-pyridinyl)-cyclopropanecarzoxamide, N- 2,2,2-trichoro-1-[(chloroacetyl)-anino]-ethyl ]-benzanide, N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide, N-formyl-N-hydroxy-DL-alanine sodium salt, ◯,◯-diethyl [2-(dipropylamlitio)-2-oxoethlyl]-ethylphosphoramidothioate, ◯-methyl S-phenyl phenylphosphoramidothioate, S-methyl 1,2,3-benzothiadiazole-7-carbothioate, spiro[2H]-1-1 -benzopyranr-2,1′(3′H)-isobenzofuran]-3′-one,

[0050] Bactericides:

[0051] bromopol, dichloroplien, nitrapyrin, nickel dimietlhylditliocarbarnate, kasugamycin, octhliinoaie, furancarhoxylic acid, oxytetracyclin, probeiiazole, strcptomycin, tecloftalam, copper sulphiate and other copper preparations.

[0052] Insecticides/Acaricides/Nematicides:

[0053] abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avernectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin, Bacillus thuringiensis, 4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(tri-fluoromethyl)-1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthirin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenotlhion, carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinplhos, chlorfluazuron, chlormephos, N-[(6-chloro-3-pyridinyl)-methyl]-N′-cyano-N-methyl-etlianimidamide, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypernethrin, cyromazine, deltamethrin, demeton M, demeton S, demeton S-methyl, diafenthiuron, diazinon, dichlofentliion, dichliorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxatlhion, disulfoton, edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimpllos, fenamiphos, fenazaquin, fenbutatin oxide, feiiitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropatlnrin, fenpyrad, fenpyroximiiate, fenthion, fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron, flucyihriinate, flufenoxuron, flufenprox, fluvalinate, fonophos, fonnothion, fosthiazate, fubferiprox, furathiocarb, IICII, hepteniophios, hexaflurnuron, hexythiazox, irnidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivernectin, lambda-cylhalothlrin, lufenLuron, malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, nitenpyram, omethoate, oxamyl, oxydemthon M, Oxdeprofos parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, salithion, sebufos, silafluofen, sulfotep, suiprofos, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, tlhiafenox, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, zetamethrin.

[0054] It is also possible to admix other known active compounds, such as herbicides, fertilizers and growth-regulating substances.

[0055] The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by pouring, spraying, atomizing, spreading, dusting, foaming, bnishilg on and the like. It is further possible to apply the active compounds by the ultra-low volume method or to inject the active compound formulation, or the active compound itself, into the soil. The seeds of the plants can also be treated.

[0056] When using the active compounds according to the invention as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g/ha, prefcrably between 10 and 1000 g/ha. In the treatment of seeds, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably bctwecn 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the active compound application rates are generally between 0.1 and 10,000 gha, preferably between 1 and 5000 g/ha.

[0057] The compositions used for protecting industrial materials generally comprise the active compounds in an amount of from 1 to 95% by weight, preferably from 10 to 75% by weight.

[0058] The use concentrations of the active compounds according to the invention depend on the species and the occurrence of the microorganisms to be controlled, and on the composition of the material to be protected. The optimum amount to be used can be determined by test series. In general, the use concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.

[0059] It is possible to increase the activity and the activity spectrum of the active compounds to be used according to the invention in the protection of materials, or of the compositions, concentrates or, quite generally, formulations preparable therefrom, by adding, if appropriate, other antimicrobially active compounds, fungicides, bactericides, herbicides, insecticides or other active compounds to increase the activity spectrum or to obtain effects, such as, for example, additional protection against insects. These mixtures may have a broader activity spectrum than the compounds according to the invention.

[0060] The preparation and the use of active compounds according to the invention are illustrated by the examples below.

[0061] Preparation examples

EXAMPLE 1

[0062]

[0063] At room temperature and with stirring, a solution of 110 mg (0.97 mmol) of 3-ethoxy-propyl isocyanate in 5 ml of absolute tetrahydrofuran is added dropwise to a mixture of 350 mg (0.97 mmol) of 3-(2-chloro-phenyl)-2-(4-fluoro-phenyl)-2-[(4,5-dilhydro-5-thiono-1,2,4-triazol-1-yl)-methyl]-oxirane, 0.1 ml of triethylamine and 5 ml of absolute tetrahydrofuran. After the addition has ended, the reaction mixture is heated at 60° C. for one hour and then concentrated under reduced pressure. The product that remains is chromatograplhed over silica gel using a mixture of cyclohexane/ethyl acetate =4:1. Concentration of the eluate gives 390 mg (82% of theory) of the substance of the formula shown above. ¹H-NMR spectrum (300 MHz, CDCI₃, TMS):

[0064] δ=10.0 (s, 1H); 8.4 (s, 1H); 7.6-7.3 (m, 6H); 7.0 (t, 2H, J=8.7 Hz); 5.1 )d, 1H,

[0065] J=14.9 Hz); 4.1 (s, 1H); 3.7 (d, 1H, J=14.9 Hz); 3.5-3.4 (m, 6H); 1.9-1.8 (m,

[0066] 2H); 1.2 (t, 3H, J=7.0 Hz) ppm.

[0067] The compounds listed in the table below are likewise prepared by the method shown in Example 1: TABLE 2 (I)

Example Melting point No. R¹ R² R³ in ° C. 2

—CH₂—CH₂—O—CH₃ 105-107 3

—CH(CH₃)₂ 104-106 4

—C₁₂H₂₅-n 53-57 5

—CH(CH₃)₂ 100-101 6

—CH₂—CH₂—O—CH₃ 96-98

EXAMPLE 7

[0068]

[0069]¹H-NMR spectrum (400 MHz, CDCl₃, TMS): δ=7.8 (s, 1H); 7.3-7.1 (m, 4H); 7.0-6.9 (m, 4H); 6.7 (s, 1H);5.0 (d, 1H); 4.5 (s, 1H); 3.7 (m, 1H); 1.0 (d, 6H, J=6.6 Hz) ppm.

[0070] Use examples

[0071] EXAMPLE A

[0072] Erysiphe test (barley)/protective Solvent: 25 parts by weight of N,N-dimethylacetamide Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

[0073] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

[0074] To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate.

[0075] After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. hordei.

[0076] The plants are placed in a greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.

[0077] Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, vhereas an efficacy of 100% means that no infections are observed.

[0078] Active compounds, application rates and test results are shown in the table below. TABLE A Erysiphe test (barley)/protective Active compound application rate Active compound g/ha Efficacy in % According to the invention: (1)

125 100 (2)

125 100 (3)

125 100 (4)

125 100

[0079] EXAMPLE B

[0080] Erysiplie test (barley)/curative Solvent: 25 parts by weight of N,N-dimethylacetamide Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

[0081] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

[0082] To test for curative activity, young plants are dusted with spores of Erysiphe graminis f.sp. hordei. 48 hours after the inoculation, the plants are sprayed with the preparation of active compound at the stated application rate.

[0083] The plants are placed in a greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.

[0084] Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infections are observed.

[0085] Active compounds, application rates and test results are shown in the table below. TABLE B Erysiphe test (barley)/curative Active compound application rate Active compound g/ha Efficacy in % According to the invention: (1)

250 100 (4)

250 100

[0086] EXAMPLE

[0087] Erysiphe test (wheat)/protective Solvent: 25 parts by weight of N,N-dimethylacetamide Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

[0088] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

[0089] To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate.

[0090] After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. tritici.

[0091] The plants are placed in a greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.

[0092] Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infections are observed.

[0093] Active compounds, application rates and test results are shown in the table below. TABLE C Erysiphe test (wheat)/protective Active compound application rate Active compound g/ha Efficacy in % According to the invention: (1)

250 100 (3)

250 100 (4)

250 100

[0094] EXAMPLE D

[0095] Leptosphaeria nodorum test (wheat)/protective Solvent: 25 parts by weight of N,N-dimethylacetamide Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

[0096] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

[0097] To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are dusted with a spore suspension of Leptosphaeria nodorum. The plants remain in an incubation cabin at 20° C. and 100% relative atmospheric humidity for 48 hours.

[0098] The plants are placed in a greenhouse at a temperature of approximately 15° C. and a relative atmospheric humidity of 80%.

[0099] Evaluation is carried out 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infections are observed.

[0100] Active compounds, application rates and test results are shown in the table below. TABLE D Leptosphaeria nodorum test (wheat)/protective Active compound application rate Active compound g/ha Efficacy in % (1)

250 100

[0101] EXAMPLE E

[0102] Puccinia test (wheat)/curative Solvent: 25 parts by weight of N,N-dimethylacetamide Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

[0103] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

[0104] To test for curative activity, young plants are sprayed with a Conidia suspension of Puccinia recondite. The plants remain in an incubation cabin at 20° C. and 100% relative atmospheric humidity for 48 hours. The plants are then sprayed with the preparation of active compound at the stated application rate.

[0105] The plants are placed in a greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80% to promote the development of rust pustules.

[0106] Evaluation is carried out 10 days after tile inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infections are observed.

[0107] Active compounds, application rates and test results are shown in the table below. TABLE E Puccinia test (wheat)/curative Active compound application rate Active compound g/ha Efficacy in % According to the invention: (1)

125 100 (2)

125 100 (3)

125 100 (4)

125 100

[0108] EXAMPLE F

[0109] Puccinia test (wheat)/protective Solvent: 25 parts by weight of N,N-dimethylacetamide Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

[0110] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

[0111] To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are sprayed with a Conidia suspension of Puccinia recondita. The plants remain in an incubation cabin at 20° C. and 100% relative atmospheric humidity for 48 hours.

[0112] The plants are placed in a greenhouse at a temperature of approximately 20° C. and a relative atmospheric humidity of approximately 80% to promote the development of rust pustules.

[0113] Evaluation is carried out 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infections are observed.

[0114] Active compounds, application rates and test results are shown in the table below. TABLE F Puccinia test (wheat)/protective Active compound application rate Active compound g/ha Efficacy in % According to the invention: (1)

125 100 (2)

125 100 (4)

125 100

[0115] EXAMPLE G

[0116] Podosphaera test (apple)/protective Solvent: 47 parts by weight of acetone Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

[0117] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

[0118] To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of the causative organism of apple mildew Podosphaera leucotricha. The plants are then placed in a greenhouse at approximately 23° C. and a relative atmospheric humidity of approximately 70%.

[0119] Evaluation was carried out 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infections are observed.

[0120] Active compounds, application rates and test results are shown in the table below. TABLE G Podosphaera test (apple)/protective Active compound application rate Active compound g/ha Efficacy in % Known from WO-A 96-38440: (A)

10  1 92 57 According to the invention: (1)

10  1 100 65 (2)

10  1 100 88 (3)

10  1 100 80 (4)

10 100

[0121] EXAMPLE H

[0122] Inhibition test on giant colonies of Basidiomycetes Solvent: Dimethylsulphoxide

[0123] To produce a suitable preparation of active compound, 0.2 parts by weight of active compound are admixed to 99.8 parts by weight of the abovementioned solvent.

[0124] An agar, prepared by using malt extract peptone, is mixed in a liquid state with the preparation of active compound at the particular desired application rate. After solidification, the resultant nutrient medium is incubated at 26° C. with mycelium pieces punched out of colonies of Coriolus versicolor.

[0125] Evaluation is carried out after 3 or 7 days' storage at 26° C. by measuring the growth of the mycelium and scoring the resulting inhibition in percent in comparison to the untreated control. 0% means an inhibition of growth which corresponds to that of the untreated control, while an inhibition of growth of 100% means that no growth of mycelium is observed.

[0126] Active compounds, active compound concentrations and test results are shown in the table below. TABLE H Inhibition test on giant colonies of Basidiomycetes Inhibition in per cent of radial growth of giant colonies at 6 ppm of active compound according to Example Fungal species (1) (3) (5) Coriolus versicolor 100 100 100 

1. Oxiranyl-triazolinethioneg of the formula

in which R¹ represents alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, optionally halogen-substituted cycloalkyl having 3 to 7 carbon atoms, naphthyl or phenyl which is optionally mono-to trisubstituted by identical or different substituents from the group consisting of halogen, nitro, phenyl, phenoxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms and halogenoalkylthlio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, R² represents plienyl which is optionally mono-to trisubstituted by identical or different substituents from the grotip consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 alogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms and halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms and R³ represents alkoxyalkyl, isopropyl or n-dodecyl.
 2. Oxiranyl-triazolinethioneiof the formula (I) For (la) according to claim I in which R¹represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, fluoro-tert-butyl, difluoro-tert-butyl, cycloalkyl having three to six carbon atoms which is optionally mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine and bromine, represents naphthyl or represents phenyl which may be mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, nitro, phenyl, phenoxy, methyl, ethyl, tert-butyl, methoxy, ethoxy, trifluoromethyl, trichlioromethyl, difluoromethyl, difluoro-chloromethyl, trifluoromethoxy, difluoromethoxy and tri fluorometlhylthio, R² represents phenyl which may be mono- to trisubstituted by identical or different substituents from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethlyl, trichloromethyl, difluorometlhyl, difluoroclhlorometliyl, triluoromethoxy, difluoromethoxy and trinfluoromethyltlhio, and R³ represents alkoxyalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety and also represents isopropyl or n-dodecyl.
 3. Process for preparing oxiranyl-triazolinethiones of the formula (I) or (Ia) according to claim 1, characterized in that oxirane derivatives of the formula

in which R¹ and R² are each as defined above are reacted with isocyanates of the formula R³-NCO  (III) in which R³ is as defined above, if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent.
 4. Microbicidal compositiorns, characterized in that they comprise at least one oxiranyl-triazolinethione of the formula (I) or (Ia) according to claim 1, in addition to extenders and/or surfactants.
 5. Use of oxiranyl-triazoline,liioiies of the formula (I) or (Ia) according to claim 1 as microbicides in crop protection and in the protection of materials.
 6. Method for controlling undesirable microorganisms in crop protection and in the protection of materials, characterized in that oxiranyl-tnazolinethmones of and/or their habitat.
 7. Process for preparing microbioidal compositions, characterized in that the oxiranyl-triazolinethiona of the formula (I) or (Ia) according to claim 1 are mixed with extenders and/or surfactants.
 8. Oxiranyl-triazolinethione according to claim 1, characterized by the formula


9. Oxiranyl-triazolinethione according to claim 1, characterized by the formula


10. Oxiranyl-triazolinethione according to claim 1, characterized by the formula 